Systems and preparations for bio-based polyurethane foams

ABSTRACT

The present invention consists of a series of bio-based polyurethane foams related to the use of such polyurethane foams for use in residential and commercial insulation industries, packaging industries and molding industries and in particular the invention includes systems and methods of manufacture and application of such bio-based polyurethane foams. The bio-based polyurethane foams are derived from castor oils, soybean oils and are not dependant on hydrocarbons, thus they are made from annually renewable natural resources.

FIELD OF THE INVENTION BACKGROUND OF THE INVENTION

In 1998, a broad cross-section of American industries, non-profit groups, trade Sep. 1, 2003 associations and academic institutions developed the “The Plant/Crop Based Renewable Resources 2020 Vision” and its follow-up, “The Technology Roadmap for Plant/Crop Based Renewable Resources 2020”; both with the objective of significantly increasing industry's use of renewable, bio-based resources.

-   -   These two documents state the long-term well being of the nation         and the maintenance of sustainable world leadership clearly         depend on the American industries' development of reliable,         renewable, bio-based resources. The major findings and         conclusions of this shared vision are:     -   To provide continued economic growth, healthy standards of         living, and strong national security for the USA, it is critical         that American industry develops plant/crop based renewable         resources that are a viable alternative to the current         dependence on nonrenewable, diminishing fossil fuels.     -   Without a renewable source of building blocks for plastic goods,         a time will come when petrochemical-derived plastic becomes too         expensive for widespread consumption.     -   The USA is overly reliant on crude oil imports, importing about         50% of our oil.     -   If imports were to cease today, the proven fossil fuel reserves         in North America would only be sufficient for 14 years at         current rates of consumption.     -   Even with existing levels of import and no increase in use, our         indigenous proven resources will only last about 28 years.     -   It is expected that as demand for consumable goods increases,         renewable resources will have to be developed to meet an         ever-increasing portion of the incremental demand.     -   Renewable resources are not directly competing with         nonrenewable; both resources will be needed to meet demands.     -   Increased market pull for sustainable, environmentally friendly         products will create powerful incentives for companies to use         and invest in plant-based building blocks.     -   American Industry's objectives must be to: Achieve at least 10%         of basic chemical building blocks from plant-derived renewable         resources by 2020 (a fivefold increase over today), with         development in place to achieve a further increase to 50% by         2050.     -   Establish bio-based systems that are economically viable, as         well as environmentally preferable.     -   Build collaborative partnerships among industry growers,         producers, academia and federal and state governments to develop         commercial applications, to revitalize rural economies and to         provide improved integration along the value-added processing         and manufacturing chain. European Union Directives on         Sustainability     -   The European Union (EU) is the recognized world leader in         addressing sustainability and environmental concerns and in         requiring greater use of environmentally preferable, bio-based         raw materials and products.     -   93/626/EEC: Council Decision of 25 Oct. 1993 on Biological         Diversity was passed to promote conservation and the sustainable         use of biological diversity, including biological resources, for         the benefit of present and future generations. It required all         European Union countries to develop and implement national         strategies, plans and programs for resource conservation and         sustainable use of biodiversity.     -   The Fifth Environmental Action Program, “Towards         Sustainability”, February 1993 defined the European Union's         policy and action programs regarding the environment and         sustainable development as follows:         -   Maintain the overall quality of life         -   Maintain continuing access to natural resources         -   Avoid lasting environmental damage         -   Consider as “sustainable” a development that meets the needs             of the present without compromising the ability of future             generations to meet their own needs.     -   The Sixth Environment Action Program, January 2001 outlines the         European Union's ambitious environmental strategy and         establishes the priorities for action on the environment for the         next five to ten years. It states that “greening the market” is         the key to sustainable development, and its stated objectives         are:         -   Better implement existing environmental laws         -   Work with business to achieve more environmentally friendly             forms of production         -   Improve resource efficiency and greater use of sustainable             resources.

FIELD OF THE INVENTION

The present invention consists of a series of bio-based polyurethane foams related to the use of such polyurethane foams for use in residential and commercial insulation industries, packaging industries and molding industries and in particular the invention includes systems and methods of manufacture and application of such bio-based polyurethane foams.

Polyurethane Insulation Foams

The use of sprayed polyurethane foam as insulation media is growing very rapidly, particularly in the home and commercial construction industries, which traditionally have standardized on fiberglass and or cellulose materials. Environmentally there are growing concerns that these materials could be considered carcinogenic and as such alternate materials are being sought. The vast majority of homebuilders use standard fiberglass “batt” insulation because it is considered cheap and quick. However inherent gaps, voids, improper fit in the stud cavity, its tendency to settle and its inability to address air leakage dramatically reduce the R-Values or thermal resistance performance of fiberglass in the wall and roof. Additionally the requirements of soffits and other ventilation and mechanical parts needed within the building add to the cost of fiberglass and cellulose insulation, thus these add to the cost, and are often taken for granted by the builder without taking account of these costs as part of the insulation needs. Today's consumer is demanding a housing product that is safe, environmentally sensitive and affordable in both the purchase and operation of the home.

Polyurethane Packaging Foam

In the packaging industries, the demand for foam is on a constant increase. This is brought about by advances in electronic devices, the explosion of the internet with usage growing at an astounding 1000 percent every three years thus creating a huge demand for communications equipment. The emerging demand for high bandwidth communications lines is growing at an even faster rate, due in part to the introduction of interactive TV, High Definition Television and more sophisticated audio and video systems. The use of polyurethane foams in packaging of sensitive products can economically protect products of any size, shape and weight; it expands in seconds to form protective cushions, expanding up to 100 times its liquid volume, thus significantly reducing the cost of storage and handling. Two 55-gallon drums of liquid components when combined can create a trailer-truck load of packaging materials.

In the Packaging Foam industries the invention will provide products that will range for uses in very light densities to protect delicate equipment and glassware to higher densities for protecting large industrial parts. Specific packaging systems will meet or exceed commercial, government and military standards.

Packaging foams can be rigid, semi-rigid, flexible, open or closed cell and may be poured by hand or used in most foam dispensing equipment for pour-in-place or pre-molded parts.

Packaging foams are primarily used for void filling; light cushioning; all purpose cushioning; extra strength cushioning; heavy duty cushioning; high performance resilient cushioning; blocking and bracing; floral arrangement medium, etc.

Polyurethane touches everyone's life, many times everyday. Polyurethane is used in wide range of products in nearly every industry . . . automobiles, construction, furniture, machinery and equipment, recreational products, consumer goods, appliances, carpeting, footwear, electronics, paints and coatings, etc.

The present invention comprises the polymers known as polyurethane's and relates to a series of foam compositions and the methods of making these foam compositions, which may be flame retardant (a substance which can be added to the polymer formulation to reduce or retard the tendency to burn). The present invention is specifically designed and formulated to replace some or all currently available expensive hydrocarbon based polyols with relatively low cost, naturally occurring and readily available Bio-based vegetable oils. The present invention further is designed as an essential part of any construction that values long-term energy savings and acoustic shielding. The foam flows easily to fill the area regardless of shape or the presence of obstructions such as pipes, wires and electrical boxes. The present invention further is designed for use in the packaging industries

BACKGROUND OF THE INVENTION

The term polyurethane refers to a thermoplastic polymer product created from the chemical reaction that results when an produced by the reaction of a polymeric isocyanate (the “A” component) and a polyol or other reactant (the “B” component) that are reactive with isocyanate, usually the hydroxyls group materials are mixed together with various cross-linkers. The polyurethane foams are formed, when mixed together by the process of simultaneous polymerization and expansion. The foam may also be tailored to variable densities, cell structures, tensile strengths and other desired physical properties. The polyurethane resins can be produced in varying forms due to properties that exhibit high elastic modulus, good electrical resistance, and high moisture resistant crystalline structures.

Due to the finite supply of fossil fuels and the high cost of energy, the need to design energy-efficient buildings that are also economical becomes important. Brick and concrete block, as high mass building materials, have the inherent energy saving feature of thermal storage capacity—or more commonly referred to as “thermal mass”. Brick and concrete block provide a unique energy efficient ‘building envelope’ due to their high thermal mass. Thermal mass is the characteristic of heat capacity and surface area capable of affecting building thermal loads by storing heat and releasing it at a later time. Materials s with high thermal mass react more slowly to temperature fluctuations and thereby reduce peak energy loads.

The polyurethane foams claimed under the present invention can be used in many applications but the present invention is aimed at the insulation market, both residential, industrial and commercial buildings. The present environment is concerned with global warming, heat conservation and reduced CFC's and HCFC's.

Some of the applications where polyurethane foam can be an effective insulation and acoustical barrier are:

Sprayed polyurethane foam under the present invention can be applied to roofing as a liquid, expanding approximately some 40 times its original liquid volume, and can be used to fill voids, cracks and crevices as well as providing an air-tight, weatherproof membrane for the roof. The foam dries in seconds following application and fully adheres to the substrate. Due to the lightweight of the foam it adds very little additional weight to the roof; the versatility of the polyurethane foam lends itself to on-site applications. Residential, commercial and industrial constructions are all candidates for polyurethane foam applications. The foam adds strength to metal and wood stud cavities due to excellent adhesion and strength to weight ratios.

Other applications where the polyurethane foam can be utilized are—corrosion protection, containment, waterproofing, perimeter wall, sound walls on interstate highways, floatation devices, spray molding, et al.

What is needed is a method of making a polyurethane product(s) from relatively inexpensive bio-based starting materials without the need to use expensive starting materials such as hydrocarbon-based polyols.

The production of the A side and the B side components, once completed can be easily mixed, the resulting liquid mixture can be sprayed or molded into the desired shape or form. The flexible polyurethane reactant foam system can be modified to produce various densities, strengths and cell structures. The procedures that can be used are identical to those employed utilizing industrial hydrocarbon based polyols.

Polymeric isocyanates which can be used in the present invention include diphenylmethane diisocyanate (MDI) [CAS number 9016-87-9], toluene 2-4 diisocyanate (2-2-TDI), naphthalene 1,5 diisocyanate (NDI), diphenylmethane 2,4′ diisocyanate (2,4′MDI); mixtures of these products may also be used. The present invention can use other ranges of isocyanates as are commonly available from manufacturers such as, BASF, Bayer, Dow Chemical Company, Huntsman etc.

Several polyurethane foams of differing rigidities and densities were prepared from different catalysts initiators, fillers and varying amounts of these ingredients. The resulting ingredients were combined in plastic containers, and thoroughly mixed. The compositions were allowed to expand freely and left to cure. Examples of this foam system are shown as examples 1 through 3.

This invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort may be had to various other embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to those skilled in the art without departing from the spirit of the present invention. For example, it is to be understood that the amounts of reagents used in the following Examples are approximate and that those skilled in the art might vary these amounts and ratios by as much as 30% without departing from the spirit of the present invention.

EXAMPLE 1

A bio-based polyurethane foam was prepared by using the following components: Ratios: A Side:B side 1:1.

“A” Side Component: Polymeric MDI (Bayer Product) 100 parts by weight

“B” Side Component: Number 1 Castor derived Polyol 17.8 parts by weight Epoxidized Soy Oil (Plascheck 775 Ferro) 34.2 parts by weight Water  8.0 parts by weight P737 (Pelron) Voranol (Dow) 12.0 parts by weight RB 79/P9457 tetrabromophthalic bromide(Pelron) 10.0 parts by weight B8870 Tegostab (Goldschmidt)  0.8 parts by weight RC 201Dibutyl tin dilaurate (Rhein Chemie)  1.0 parts by weight TCPP/P9338 Pelron (tris-(chlorisopropyl) phosphate 12.0 parts by weight RC 108 blend of a tertiary amine and dipropylene  1.5 parts by weight Glycol (Rhein Chemie) 0-500 Ortegol (Goldschmidt)  0.2 parts by weight DMEA Dimethylethanol amine (Rhein Chemie)  2.5 parts by weight

-   -   The “B” side components are mixed together in a suitable mixing         vessel using a specially designed high shear mixer and blending         the components for a period of fifteen minutes.

Following the preparation of the B side, the two components were mixed together in a container for about 30 seconds. The reaction of side A with side B resulted in the immediate formation of foam cells, which were allowed to freely rise within to the container. The foam cells bonded to all surfaces of the container and the resultant foam remained “tacky” for approximately 3 minutes until completely cured. The resulting foam possessed good adherence properties, suitable for a applications of insulation. The formulation is unique in that the density of the resultant foam was 1.0 pounds per cubic foot, using water as the blowing agent, forming a product that can be classed as “an open/closed” cell polyurethane bio-based foam. The system when combined as the two components A and B results in a bio-based product containing twenty six percent naturally derived vegetable based polyols. Slight variations of the components in the “B” side can be made to change the range of densities and thermal components.

EXAMPLE 2

A bio-based polyurethane foam was prepared by using the following components: Ratios: A Side:B Side 1:1

“A” Side Component: Polymeric MDI (Bayer Product) 100.0 parts by weight

B” Side Component: Number 1 Castor derived polyol 28.0 parts by weight H 360 Sucrose Polyol (Harvin)[P9157 Pelron] 23.0 parts by weight Water  3.5 parts by weight DMEA Dimethylethanol amine (Rhein Chemie)  3.0 parts by weight B8870 Tegostab (Goldschmidt)  0.8 parts by weight RC 201 Dibutyl tin dilaurate (Rhein Chemie)  0.5 parts by weight 470X (P737) Voranol (Pelron) 28.0 parts by weight RC 108 blend of a tertiary amine and dipropylene  1.2 parts by weight Glycol (Rhein Chemie) TCPP/P9338 (tris-(chlorisopropyl) phospate(Pelron) 12.0 parts by weight

-   -   The “B” side components are mixed together in a suitable mixing         vessel using a specially designed high shear mixer and blending         the components for a period of fifteen minutes.     -   Following the preparation of the B side, the two components were         mixed together in a container for about 30 seconds. The reaction         of side A with side B resulted in the immediate formation of         foam cells, which were allowed to freely rise external to the         container. The foam cells bonded to all surfaces of the         container and the resultant foam remained “tacky” for         approximately 3 minutes until completely cured. The resulting         foam possessed good adherence properties, suitable for closed         cell insulation purposes. The density of the resultant foam was         1.7 pounds per cubic foot using water as the blowing agent.         Slight variations of the components in the “B” side can be made         to change the range of densities and thermal components.

EXAMPLE 3

A bio-based polyurethane foam was prepared by using the following components: Ratios: A Side:B Side 1:1

“A” Side Component: Polymeric MDI (Bayer Product) 100.0 parts by weight

“B” Side Component: Number 1 Castor derived polyol 33.0 parts by weight Epoxidized Soy Oil Plascheck 775 (Ferro)  4.0 parts by weight Water 20.0 parts by weight RC 108 blend of a tertiary amine and dipropylene  2.5 parts by weight Glycol (Rhein Chemie) RC 201 Dibutyl tin dilaurate (Rhein Chemie)  1.0 parts by weight RB79/P9457 (Pelron) 12.0 parts by weight TCPP/P9338 (tris-(chlorisopropyl) 22.0 parts by weight phosphate(Pelron) B8870 Tegostab (Goldschmidt)  1.5 parts by weight 0-500 Ortegol (Goldschmidt)  1.5 parts by weight TEA Triethanol Amine  2.5 parts by weight

-   -   The “B” side components are mixed together in a suitable mixing         vessel using a specially designed high shear mixer and blending         the components for a period of fifteen minutes.     -   Following the preparation of the B side, the two components were         mixed together in a container for about 30 seconds. The reaction         of side A with side B resulted in the immediate formation of         foam cells, which were allowed to freely rise external to the         container. The foam cells bonded to all surfaces of the         container and the resultant foam remained “tacky” for         approximately 3 minutes until completely cured. The resulting         foam possessed good adherence properties, suitable for         insulating when an “open” cell foam is desired. The density of         the resultant foam was 0.5 to 0.6 pounds per cubic foot. The         system when combined as the two components A and B results in a         bio-based product containing eighteen point five percent         naturally derived vegetable based polyols. Slight variations of         the components in the “B” side can be made to change the range         of densities and thermal components, an example being the         addition of small amounts of cyclopentane.     -   It should be understood, of course, that the foregoing relates         only to preferred embodiments of the present invention and that         numerous modifications or alterations may be made therein         without departing from the spirit and the scope of the         invention. 

1. A group of compositions (solutions) as defined hereunder that produces a series of polyurethane foams comprising of bio-based polyols, hydroxl groups, and water, along with amine catalysts and monomers and surfactants.
 2. A composition as in claim 1, wherein: A. one water-insoluble, unsaturated hydroxyl acid C₁₈H₃₄O₃ comprising an oil formed from castor beans; B. adding an epoxidized oleochemical derived from soybean, such oleochemical oil-base polyol having a hydroxyl content of about 110 mg KOH/g of polyol to about 200 mg KOH/g of polyol [example 1].
 3. A polymeric composition as in claim 1, further comprising a polyurethane, having: at least two bio-based oils [castor, soyoil]; at least one triol polyol [Voranol] at least one surfactant B8870; at least one stabilizer bromide RB 79; at least one solvent, cross-linker RC201; at least one fire retardant [TCPP]; at least one drying agent, catalyst [RC108]; at least one cell opener [0-500] at least one stabilizer; [DMEA]
 4. A composition as in claim 1 wherein the uses of bio-based polyols provide a bio-based content of the reacted components of having at least twenty six percent bio-based (26%) content.
 5. A composition as in claim 1, wherein: A. one water-insoluble, unsaturated hydroxyl acid C₁₈H₃₄O₃ comprising an oil formed from castor beans; B. adding a sucrose based polyol, such having a hydroxyl content of about 300 mg KOH/g of polyol to about 350 mg KOH/g of polyol [example 2].
 6. A polymeric composition as in claim 5, further comprising a polyurethane, having: at least two bio-based oils [castor, sucrose]; at least one stabilizer; [DMEA;] at least one surfactant B8870; at least one solvent, cross-linker RC201; at least one triol polyol [Voranol]; at least one drying agent, catalyst [RC108]; at least one fire retardant [TCPP];
 7. A composition as in claim 5 wherein the uses of bio-based polyols provide a bio-based content of the reacted components of having at least nineteen percent bio-based (19%) content.
 8. A composition as in claim 1, wherein: A. one water-insoluble, unsaturated hydroxyl acid C₁₈H₃₄O₃ comprising an oil formed from castor beans; B. adding an epoxidized oleochemical derived from soybean, such oleochemical oil-base polyol having a hydroxyl content of about 110 mg KOH/g of polyol to about 200 mg KOH/g of polyol [example 3].
 9. A polymeric composition as in claim 8, further comprising a polyurethane, having: at least two bio-based oils [castor, soyoil]; at least one drying agent, catalyst [RC108]; at least one solvent, cross-linker RC201; at least one stabilizer bromide RB 79; at least one fire retardant [TCPP]; at least one surfactant B8870; at least one cell opener [0-500]; at least one stabilizer; [TEA].
 10. A composition as in claim 8 wherein the uses of bio-based polyols provide a bio-based content of the reacted components of having at least fifteen percent bio-based (15%) content.
 11. The polymer composition of claim 1, wherein the at least one isocyanate comprising 4,4′-dephenyl methane diisocyanate (MDI) wherein the MDI comprises by weight between about 50% of the polymer composition.
 12. A polymeric composition as in claim 1, further comprising a polyurethane, having at least two component parts comprising: Side A Component at least one ester of isocyanic acid Side B Component at least one bio-based oil a specific amount of filtered water to react with the isocyanate to form carbon dioxide (the primary gas for expansion of the foam). 